EP2920330B1 - Recovering lead from a mixed oxidized material - Google Patents
Recovering lead from a mixed oxidized material Download PDFInfo
- Publication number
- EP2920330B1 EP2920330B1 EP13812067.0A EP13812067A EP2920330B1 EP 2920330 B1 EP2920330 B1 EP 2920330B1 EP 13812067 A EP13812067 A EP 13812067A EP 2920330 B1 EP2920330 B1 EP 2920330B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lead
- mixed oxidized
- sulfonic acid
- liquid leachate
- methane sulfonic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims description 41
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 149
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 73
- 239000007788 liquid Substances 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 32
- 238000002386 leaching Methods 0.000 claims description 21
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 claims description 16
- 229910000003 Lead carbonate Inorganic materials 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 239000012141 concentrate Substances 0.000 claims description 13
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- LLABTCPIBSAMGS-UHFFFAOYSA-L lead(2+);methanesulfonate Chemical class [Pb+2].CS([O-])(=O)=O.CS([O-])(=O)=O LLABTCPIBSAMGS-UHFFFAOYSA-L 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229910000464 lead oxide Inorganic materials 0.000 claims description 5
- 238000000638 solvent extraction Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 238000010979 pH adjustment Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000005273 aeration Methods 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000010951 particle size reduction Methods 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 239000012535 impurity Substances 0.000 description 13
- 238000011084 recovery Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052924 anglesite Inorganic materials 0.000 description 7
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- -1 PbO) Chemical compound 0.000 description 4
- 229910006069 SO3H Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000005363 electrowinning Methods 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910017113 AlSi2 Inorganic materials 0.000 description 1
- 241001116389 Aloe Species 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910000007 Leadhillite Inorganic materials 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000184 acid digestion Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000011399 aloe vera Nutrition 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 238000009291 froth flotation Methods 0.000 description 1
- 229910000743 fusible alloy Inorganic materials 0.000 description 1
- 229910052949 galena Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229910000698 pewters Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- Lead is used in a variety of applications, including, for example, building construction, energy storage batteries (e.g., lead-acid batteries), weaponry (e.g., bullets, shots, etc.), and alloy materials (e.g., solders, pewters, fusible alloys, etc.). With such widespread application, annual lead production has expanded to greater than four million tons of refined metal. Lead may be recovered from natural ores (e.g., in a variety of mineral forms) or from recycling processes. Some lead recovery processes involve ore mining, froth flotation (which produces a high grade lead concentrate), smelting of the lead concentrate (which produces crude lead metal), and refining of the crude lead metal. Lead recovery processes involving smelting often use high temperatures, which may generate volatile products that are difficult to control and/or contain.
- energy storage batteries e.g., lead-acid batteries
- weaponry e.g., bullets, shots, etc.
- alloy materials e.g., solders, pewters, fusible alloys
- WO 2007/099119 relates to a process for the acid digestion of metal-containing compounds by leaching by means of an aqueous leachant, wherein the aqueous leachant i) contains an alkansulphonic acid and, if appropriate, sulphuric acid and/or surfactant and/or ii) a mixture of an alkanesulphonic acid salt and sulphuric acid and also, if appropriate, surfactant.
- an aqueous leachant containing one or more alkanesulphonic acids and, if appropriate, sulphuric acid and/or surfactant and also an aqueous leachant containing one or more alkanesulphonic acid salts and sulphuric acid and, if appropriate, surfactant are also provided.
- the present disclosure relates generally to recovering lead from a mixed oxidized material.
- Examples of the method disclosed herein utilize methane sulfonic acid (MSA) for recovering lead from mixed oxidized lead materials, such as materials containing lead oxide (i.e., PbO), lead carbonate (i.e., cerussite or PbCO 3 ), and/or lead sulfate (e.g., anglesite or PbSO 4 ).
- MSA methane sulfonic acid
- PbO lead oxide
- PbCO 3 lead carbonate
- lead sulfate e.g., anglesite or PbSO 4
- the mixed oxidized lead material MOPbM may be a mixed oxidized ore of lead or a mixed oxidized concentrate of lead, either of which includes one or more of lead oxide, lead carbonate, and lead sulfate.
- the mixed oxidized concentrate of lead may be formed from a mixed oxidized ore of lead.
- the mixed oxidized lead material MOPbM Prior to performing the recovery method(s) disclosed herein, the mixed oxidized lead material MOPbM may be subjected to a particle size reduction process (i.e., comminution).
- the particle size of the mixed oxidized lead material MOPbM range anywhere from 10 ⁇ m to about 500 ⁇ m.
- the reduced particle size may range anywhere from 50 ⁇ m to about 100 ⁇ m.
- Comminution may be accomplished by crushing, grinding, or another suitable size reduction process. The reduction in size may lead to increased reactivity of the lead material MOPbM and increased lead extraction efficiency.
- methane sulfonic acid (CH3S03H, also referred to herein as MSA) is selected as a leaching agent for the process.
- the selection of methane sulfonic acid is shown as "MSA" in Fig. 1 .
- Methane sulfonic acid is a strong organic acid that is virtually free of metal ions and sulfates. It has been found that lead is highly soluble in methane sulfonic acid. For example, lead has a solubility of 143 g per 100 g of methane sulfonic acid in solution. As such, it is particularly desirable to select this acid for the lead recovery method(s) 10 disclosed herein.
- the lead recovery method(s) 10 utilizing MSA surprisingly involved a speedy leach extraction (e.g., from about 10 minutes to about 120 minutes) and completeness of the reaction.
- the methane sulfonic acid is used in an aqueous solution including from about 0.01 wt.% MSA to about 30 wt.% MSA, and a balance of water.
- the aqueous solution may include water and from about 0.05 wt.% MSA to about 10 wt.% MSA, or water and from about 0.25 wt.% MSA to about 5 wt.% MSA.
- the aqueous solution may be made by diluting a concentrated form of the MSA with a desirable amount of water.
- the methane sulfonic acid is LUTROPUR® MSA or LUTROPUR® MSA 100 (both of which are commercially available from BASF Corp., located in Florham Park, NJ), and a suitable amount of water is added to the more concentrated form of MSA to obtain the solution having the desired MSA weight percent.
- the solution including methane sulfonic acid may be referred to herein as the MSA solution.
- the mixed oxidized lead material MOPbM is exposed to the MSA solution. Exposure of the mixed oxidized lead material MOPbM to the MSA solution involves contacting the solid mixed oxidized lead material MOPbM with the liquid MSA solution. Solid-liquid contact may be accomplished by heap leaching, vat leaching, dump leaching, or by pulping the mixed oxidized lead material MOPbM with the MSA solution. The mixed oxidized lead material MOPbM is mixed with the MSA solution to produce a suspension. Exposure of the mixed oxidized lead material MOPbM to the MSA solution initiates acid leaching of lead from lead oxide and/or lead carbonate present in the mixed oxidized lead material MOPbM, and generates a liquid leachate.
- the amount of the mixed oxidized lead material MOPbM and the amount of the MSA solution used may depend upon a target lead concentration for the liquid leachate formed during the step shown at reference numeral 12 of the method 10.
- the solid to liquid (i.e., MOPbM to MSA solutior:i) ratio is selected so that the resulting liquid leachate has a lead concentration that is sufficient for performing lead electrolysis.
- the target lead concentration in the liquid leachate ranges from about 5 g Pb/L leachate up to saturation.
- the target lead concentration in the liquid leachate is 50 g Pb/L leachate.
- the target lead concentration may vary depending, at least in part, upon the strength of the MSA solution to be used and the temperature to be used during leaching.
- the solid to liquid ratio is selected so that the suspension of MOPbM in the MSA solution includes from about 1 % solids to about 50% solids.
- the composition of the MSA solution may also be selected to match the target lead concentration.
- one molecule of MSA may be provided for each molecule of lead that is to be dissolved. It may also be desirable that excess MSA be present in order to maintain a minimum level of free acid in solution. As such, approximately 0.47 g of MSA may be used per gram of lead to be leached.
- the mixed oxidized lead material MOPbM includes about 50% lead and the target concentration is 500 g of lead per liter of leachate, then the amount of MSA in the MSA solution may be about 118 g MSA/L.
- the suspension of the mixed oxidized lead material MOPbM and MSA solution may be maintained at a predetermined temperature for a predetermined time as the liquid leachate is allowed to form.
- the predetermined temperature may range anywhere from about 10°C to about 100°C or the boiling point of water. In an example, the predetermined temperature ranges from about 10°C to about 80°C. In another example, the predetermined temperature may range anywhere from about 20°C to about 50°C.
- the temperature of the suspension may be increased to some temperature at the higher end of the given ranges in order to accelerate the rate and extent of the lead leaching.
- the time for maintaining the suspension may be any time that is sufficient to extract a desirable amount of the soluble lead from the mixed oxidized lead material MOPbM. In an example, the time ranges from about 10 minutes to about 120 minutes.
- the suspension may also be stirred. Stirring may be accomplished using any suitable mechanism including a baffle-stirred reactor, a magnetic stirrer, etc.
- the liquid leachate that is formed includes water and a lead-methane sulfonate salt that is soluble in the water.
- the lead-methane sulfonate salt is the product of acid leaching of the lead oxide and/or lead carbonate originally present in the mixed oxidized lead material MOPbM. Reactions that may take place during the formation of the liquid leachate include: PbO + 2CH 3 SO 3 H ⁇ Pb(CH 3 SO 3 ) 2 + H 2 O PbCO 3 + 2CH 3 SO 3 H ⁇ Pb(CH 3 SO 3 ) 2 + H 2 O + CO 2 (g).
- the first reaction involves the lead oxide (PbO) reacting with the methane sulfonic acid (CH 3 SO 3 H) to generate the lead-methane sulfonate salt (Pb(CH 3 SO 3 ) 2 ) and water.
- the second reaction involves the lead carbonate (PbCO 3 ) reacting with the methane sulfonic acid (CH 3 SO 3 H) to generate the lead-methane sulfonate salt Pb(CH 3 SO 3 ) 2 , water, and carbon dioxide (in gas form).
- the liquid leachate may also include a solid material, i.e., a leach solid or residue.
- the liquid leachate may be exposed to a solid-liquid separation process (shown at reference numeral 14 of Fig. 1 ).
- Solid-liquid separation may be accomplished using thickening, filtration, centrifugation, cycloning, or another like technique in combination with washing.
- the solid-liquid separation results in the separation of the leach solid/residue from the liquid leachate.
- the use of the leach solid/residue will be discussed further hereinbelow in reference to reference numerals 22 through 26 of Fig. 1 .
- the liquid leachate may still contain impurities.
- the step shown at reference numeral 16 of Fig. 1 involves purifying the liquid leachate.
- Reagent(s) R may be added to the liquid leachate in order to remove impurities I.
- the reagent R include pH adjusting agents or metallic lead powder or scrap.
- purification of the liquid leachate is accomplished using pH Adjustment, with or without aeration, to oxidize and hydrolyze impurities, such as iron, aluminum, chromium, etc.
- suitable pH adjusting agents include lead carbonate, sodium hydroxide, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, and sodium carbonate.
- the pH adjusting agent may be added in any amount that is sufficient to achieve a desirable pH value.
- the pH adjusting agent may be added to the liquid leachate until the pH of the leachate is at the target value.
- iron carbonate is present in the mixed oxidized lead material MOPbM prior to MSA solution leaching, iron will extract with the lead into the liquid leachate, as shown in the following reaction: FeCO 3 + 2CH 3 SO 3 H ⁇ Fe(CH 3 SO 3 ) 2 + H 2 O + CO 2 (g).
- the iron can be removed by pH adjustment using an excess of lead carbonate and oxidation with air or oxygen.
- the removal of iron by pH adjustment is shown in the following reaction: 4Fe(CH 3 SO 3 ) 2 + O 2 (g + 2PbCO 3 + 6H 2 O ⁇ 2(CH 3 SO 3 ) 2 + 4Fe(OH) 3 .
- cementation may be used to purify the liquid leachate.
- metallic lead powder or scrap is used to precipitate other noble metals, such as copper.
- the amount of metallic lead powder or scrap used will depend, at least in part, on the amount of impurities to be removed. In an example, the amount of metallic lead powder or scrap is proportional to the amount of impurities to be removed. As such, it may be desirable to use near stoichiometric amounts. Depending upon the metal impurity to be removed, it may also be desirable to include an excess of the metallic lead powder or scrap (i.e., an amount above the stoichiometric amount).
- purification may also be accomplished with solvent extraction, ion exchange, or precipitation (e.g., sulfide precipitation) so as to remove the impurities I and produce a purified liquid leachate that is suitable for electrolysis.
- solvent extraction ion exchange, or precipitation (e.g., sulfide precipitation) so as to remove the impurities I and produce a purified liquid leachate that is suitable for electrolysis.
- precipitation e.g., sulfide precipitation
- Solvent extraction may be accomplished by mixing an organic solution containing the extractant with the aqueous liquid leachate. Mixing extracts the impurity into the organic phase.
- the solvent extraction reagents may vary depending upon the type of impurity to be removed. Some examples of suitable solvent extraction reagents include di-2-ethyl-hexyl-phosphoric acid and similar phosphonic or phosphinic acids, salicylaldoxime, mixtures including salicylaldoxime, VERSATICTM acids (i.e., highlybranched carbon-rich molecules with vinyl ester, glycidyl ester, acrylate, hydroxyl and/or carboxylic functionality, from Momentive Specialty Chemicals, Gahanna, OH), etc.
- suitable solvent extraction reagents include di-2-ethyl-hexyl-phosphoric acid and similar phosphonic or phosphinic acids, salicylaldoxime, mixtures including salicylaldoxime, VERSATICTM acids (i.e.,
- the two solutions are separated, for example, by gravity settling. At this point, the organic solution is loaded with the impurity, and this solution may be exposed to stripping. The purified aqueous liquid leachate may then be used in electrolysis.
- an ion exchange resin is contacted with the impure liquid leachate in a column or in a stirred reactor.
- Suitable ion exchange resins may include strong acid exchangers or chelating type exchangers.
- a chemical precipitant is added to the liquid leachate to precipitate the impurity as a solid particle.
- the solid particle impurities are removed using any suitable technique, such as filtering, thickening (e.g., gravity settling and washing), or the like.
- chemical precipitants that form sulfide precipitants include hydrogen sulfide gas, sodium hydrosulfide, calcium sulfide, sodium sulfide, etc.
- any suitable purification method may be used to selectively remove impurities I that are present in the liquid leachate, so long as the soluble lead-methane sulfonate salt remains in solution.
- electrolysis may be accomplished in an undivided electrochemical cell 30 containing an anode 32 and a cathode 34. While a single anode 32 and cathode 34 are shown, it is to be understood that a single cell 30 may include multiple anodes 32 and cathodes 34. Examples of materials suitable for the anodes 32 include graphite, titanium structures coated with precious metal oxides (i.e., DSA anodes), or any other anode material. Examples of materials suitable for the cathodes 34 include lead, stainless steel, similar recyclable materials, or any other cathode material.
- the purified liquid leachate is introduced into the cell 30 and functions as an electrolyte 36.
- the electrodes 32, 34 may be connected to a power supply 38 via an external circuit 40.
- the power supply 38 and circuit 40 allow electric current and electrons (e-) to flow between the electrodes 32, 34.
- current is supplied to the anode 32 at a current density ranging from about 100 A/m2 to about 1000 A/m2. The current density may be varied depending, at least in part, on the configuration of the cell 30.
- the power supply 38 delivers direct current (DC) to the anode 32, and electrowinning is initiated.
- electrowinning the current is passed from the anode 32 through the purified liquid leachate (i.e., the electrolyte 36) which contains the lead.
- the purified liquid leachate i.e., the electrolyte 36
- ionic current flows in solution. Cations are attracted to the cathode 34 and anions are attracted to the anode 32, and thus are conducted by the voltage gradient in solution between the electrodes 32, 34.
- the lead is extracted as it is deposited, in an electroplating process, onto the cathode 34.
- the overall chemical reaction in the cell 30 is: Pb(CH 3 SO 3 ) 2 + H 2 O ⁇ Pb + 2CH 3 SO 3 H + 1 ⁇ 2 O 2 (g) where the following reactions take place at the anode and cathode, respectively: H 2 O ⁇ 1 ⁇ 2 O 2 (g) + 2H + + 2e - Pb(CH 3 SO 3 ) 2 + 2e - ⁇ Pb + 2CH 3 SO 3 - .
- lead is recovered as metal at the cathode 34 and oxygen is evolved at the anode 32 by electrolyzing the purified lead methane sulfonate solution (i.e., Pb(CH 3 SO 3 ) 2 ).
- the electrolyte 36 i.e., the purified liquid leachate
- the lead-depleted, methane sulfonic acidcontaining electrolyte 36 may be recycled and used in the MSA solution in another cycle of lead recovery.
- some amount of concentrated MSA may be added in order to generate a new MSA solution including from about 0.01 wt.% methane sulfonic acid to about 30 wt.% methane sulfonic acid.
- Electrolysis and electrowinning may be performed for any desirable amount of time in order to extract the lead from the electrolyte 36.
- electroplating is allowed to take place for a period ranging from about 1 day to about 7 days. This may generate relatively thick deposits of pure lead on the cathode 34.
- the temperature of the cell 30 during electrolysis may range from ambient temperature (e.g., 20°C) to about 80°C. In an example, the temperature of the cell 30 is maintained from about 35°C to about 45°C.
- Electrochemical additives such as animal glue, lignin sulfonates, aloes, etc. may be added to the cell 30 in order to smooth the cathode deposit and minimize contamination.
- the amount of any electrochemical additive added may be less than 1 g/L of solution and less than 1 kg/t (i.e., tonnes or metric tons) of metal plated.
- the method 10 may further include additional steps in which the separated leach solid/residue is utilized. These additional steps may be particularly desirable when lead sulfate is present in the original mixed oxidized lead material MOPbM.
- the lead sulfate is not leached during acid leaching (i.e., at the step shown at reference numeral 12 in Fig. 1 ), at least in part, because lead sulfate is essentially insoluble in the MSA solution.
- the lead sulfate may be converted to lead carbonate, which can be recycled in an MSA solution in another cycle of lead recovery.
- the separated leach solid/residue that is recovered as a result of solid-liquid separation of the liquid leachate is treated with a source of soluble carbonate (shown as CO 3 in Fig. 1 ).
- a source of soluble carbonate include sodium carbonate, potassium carbonate, or ammonium carbonate.
- the leach solid/residue is pulped with an aqueous solution containing the soluble carbonate source.
- Pulping may be performed i) with a high solids density and a sufficient amount of the soluble carbonate, and ii) for a time and at a temperature so that lead sulfate phases/minerals in the leach solid/residue are converted to lead carbonate.
- the ratio of carbonate in solution to sulfate in the solids is at least 1: 1 on a mole: mole basis.
- An example of the reaction that may take place when the leach solid/residue (which contains lead sulfate, PbS04) is treated with sodium carbonate as the source of soluble carbonate is as follows: PbSO 4 + Na 2 CO 3 ⁇ PbCO 3 + Na 2 SO 4 .
- the treatment of the leach solid/residue generates a second liquid leachate which includes a second leach solid/residue.
- the second liquid leachate is a sulfate solution containing a lead carbonate solid (i.e., the second leach solid/residue).
- the second liquid leachate may be exposed to a solid-liquid separation process (shown at reference numeral 24 of Fig. 1 ), which may be performed using any of the techniques previously described.
- the solid-liquid separation results in the separation of the second leach solid/residue from the second liquid leachate.
- the sulfate solution (i.e., the second liquid leachate, shown as SO 4 in Fig. 1 ) may be used in any desirable manner.
- the sodium sulfate solution may be sold as a separate by-product or used in other processes (such as in the manufacture of detergents, or in the Kraft process of paper pulping, etc.).
- the second leach solid/residue containing lead carbonate formed from lead sulfate may be recycled.
- the second leach solid/residue may be incorporated into an MSA solution (with or without additional mixed oxidized lead material MOPbM) in another cycle of lead recovery.
- a lead concentrate containing 67.12% Pb, 0.03% Zn, 1.52% Fe, 1.57% Al, 11.12% C (inorganic) and 1.5% S (total) was obtained from the Magellan Mine (Australia). X-Ray Diffraction with Rietveld Analysis was performed to identify the minerals in the concentrate.
- the particle size of the lead concentrate was -150 + 7 4 microns (i.e., greater than 74 microns and less than 150 microns), and a solution having a methane sulfonic acid concentration of 0.036 mol/L was used.
- 2 g of the lead concentrate was added to 500 ml of the methane sulfonic acid solution in a 1 L baffled stirred reactor immersed in a water bath. The mixture was stirred at 400 rpm, and the temperature was set to 25°C. The mixture was allowed to sit under these conditions. A liquid leachate was formed, and a sample of the leachate was extracted after 30 minutes. This sample was analyzed for lead. This test revealed that after 30 minutes of leaching, 85% of the lead in the concentrate was extracted into solution.
- Residue from the liquid leachate was recovered and analyzed by Rietveld XRay Diffraction.
- the residue contained 0.5% cerussite, 1.5% galena, 62.4% anglesite, 24.5% quartz, 4.8% kaolinite, and 6.3% muscovite.
- Example 2 Another MSA leaching test was performed using 10 g of the lead concentrate described in Example 1, except that the particle size was -45 +38 microns (i.e., greater than 38 microns and less than 45 microns). The MSA solution of Example 1 was utilized, except that 50% excess MSA was added. This leaching test was performed at 25°C for 1 hour.
- a leach residue was recovered, washed, and dried.
- a sodium carbonate leaching process was performed for 1 hour at 50°C with 10:1 liquid to solid ratio and a 20% excess of sodium carbonate.
- a leach residue from this process was recovered, washed, and dried.
- the overall extraction of lead for this Example was 98.04%.
- ranges provided herein include the stated range and any value or sub-range within the stated range.
- a range from about 10 ⁇ m to about 500 ⁇ m should be interpreted to include not only the explicitly recited limits of about 10 ⁇ m to about 500 ⁇ m, but also to include individual values, such as 15 ⁇ m, 120 ⁇ m, 250 ⁇ m, 400 ⁇ m, etc., and sub-ranges, such as from about 150 ⁇ m to about 450 ⁇ m, from about 200 ⁇ m to about 300 ⁇ m, etc.
- “about” is utilized to describe a value, this is meant to encompass minor variations (up to+/- 10%) from the stated value.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Description
- Lead is used in a variety of applications, including, for example, building construction, energy storage batteries (e.g., lead-acid batteries), weaponry (e.g., bullets, shots, etc.), and alloy materials (e.g., solders, pewters, fusible alloys, etc.). With such widespread application, annual lead production has expanded to greater than four million tons of refined metal. Lead may be recovered from natural ores (e.g., in a variety of mineral forms) or from recycling processes. Some lead recovery processes involve ore mining, froth flotation (which produces a high grade lead concentrate), smelting of the lead concentrate (which produces crude lead metal), and refining of the crude lead metal. Lead recovery processes involving smelting often use high temperatures, which may generate volatile products that are difficult to control and/or contain.
-
WO 2007/099119 relates to a process for the acid digestion of metal-containing compounds by leaching by means of an aqueous leachant, wherein the aqueous leachant i) contains an alkansulphonic acid and, if appropriate, sulphuric acid and/or surfactant and/or ii) a mixture of an alkanesulphonic acid salt and sulphuric acid and also, if appropriate, surfactant. Furthermore, an aqueous leachant containing one or more alkanesulphonic acids and, if appropriate, sulphuric acid and/or surfactant and also an aqueous leachant containing one or more alkanesulphonic acid salts and sulphuric acid and, if appropriate, surfactant are also provided. - Features and advantages of examples of the present disclosure will become apparent by reference to the following detailed description and drawings, in which like reference numerals correspond to similar, though perhaps not identical, components. For the sake of brevity, reference numerals or features having a previously described function may or may not be described in connection with other drawings in which they appear.
-
Fig. 1 is a schematic flow diagram depicting an example of a method for recovering lead from a mixed oxidized lead material; and -
Fig. 2 is a schematic illustration of an undivided electrochemical cell for performing an electrolysis step of an example of the method for recovering lead from a mixed oxidized lead material. - The present disclosure relates generally to recovering lead from a mixed oxidized material. Examples of the method disclosed herein utilize methane sulfonic acid (MSA) for recovering lead from mixed oxidized lead materials, such as materials containing lead oxide (i.e., PbO), lead carbonate (i.e., cerussite or PbCO3), and/or lead sulfate (e.g., anglesite or PbSO4). It has been found that the use of methane sulfonic acid in the method(s) disclosed herein enables lead recovery from various mixed oxidized lead materials while advantageously avoiding high temperature smelting and the use of other acids, which may be unstable or may introduce other undesirable issues with lead recovery.
- Referring now to
Fig. 1 , an example of themethod 10 for recovering lead from a mixed oxidized lead material is schematically depicted. In the examples disclosed herein, the mixed oxidized lead material MOPbM may be a mixed oxidized ore of lead or a mixed oxidized concentrate of lead, either of which includes one or more of lead oxide, lead carbonate, and lead sulfate. The mixed oxidized concentrate of lead may be formed from a mixed oxidized ore of lead. Prior to performing the recovery method(s) disclosed herein, the mixed oxidized lead material MOPbM may be subjected to a particle size reduction process (i.e., comminution). It is generally desirable that the particle size of the mixed oxidized lead material MOPbM range anywhere from 10 µm to about 500 µm. In an example, the reduced particle size may range anywhere from 50 µm to about 100 µm. Comminution may be accomplished by crushing, grinding, or another suitable size reduction process. The reduction in size may lead to increased reactivity of the lead material MOPbM and increased lead extraction efficiency. - At the outset of the
method 10 shown inFig. 1 , methane sulfonic acid (CH3S03H, also referred to herein as MSA) is selected as a leaching agent for the process. The selection of methane sulfonic acid is shown as "MSA" inFig. 1 . Methane sulfonic acid is a strong organic acid that is virtually free of metal ions and sulfates. It has been found that lead is highly soluble in methane sulfonic acid. For example, lead has a solubility of 143 g per 100 g of methane sulfonic acid in solution. As such, it is particularly desirable to select this acid for the lead recovery method(s) 10 disclosed herein. In addition, the lead recovery method(s) 10 utilizing MSA surprisingly involved a speedy leach extraction (e.g., from about 10 minutes to about 120 minutes) and completeness of the reaction. - In the examples disclosed herein, the methane sulfonic acid is used in an aqueous solution including from about 0.01 wt.% MSA to about 30 wt.% MSA, and a balance of water. In other examples, the aqueous solution may include water and from about 0.05 wt.% MSA to about 10 wt.% MSA, or water and from about 0.25 wt.% MSA to about 5 wt.% MSA. The aqueous solution may be made by diluting a concentrated form of the MSA with a desirable amount of water. In one example, the methane sulfonic acid is LUTROPUR® MSA or LUTROPUR® MSA 100 (both of which are commercially available from BASF Corp., located in Florham Park, NJ), and a suitable amount of water is added to the more concentrated form of MSA to obtain the solution having the desired MSA weight percent. The solution including methane sulfonic acid may be referred to herein as the MSA solution.
- At
reference numeral 12 inFig. 1 , the mixed oxidized lead material MOPbM is exposed to the MSA solution. Exposure of the mixed oxidized lead material MOPbM to the MSA solution involves contacting the solid mixed oxidized lead material MOPbM with the liquid MSA solution. Solid-liquid contact may be accomplished by heap leaching, vat leaching, dump leaching, or by pulping the mixed oxidized lead material MOPbM with the MSA solution. The mixed oxidized lead material MOPbM is mixed with the MSA solution to produce a suspension. Exposure of the mixed oxidized lead material MOPbM to the MSA solution initiates acid leaching of lead from lead oxide and/or lead carbonate present in the mixed oxidized lead material MOPbM, and generates a liquid leachate. - The amount of the mixed oxidized lead material MOPbM and the amount of the MSA solution used may depend upon a target lead concentration for the liquid
leachate formed during the step shown atreference numeral 12 of themethod 10. In an example, the solid to liquid (i.e., MOPbM to MSA solutior:i) ratio is selected so that the resulting liquid leachate has a lead concentration that is sufficient for performing lead electrolysis. In an example, the target lead concentration in the liquid leachate ranges from about 5 g Pb/L leachate up to saturation. As an example, the target lead concentration in the liquid leachate is 50 g Pb/L leachate. The target lead concentration may vary depending, at least in part, upon the strength of the MSA solution to be used and the temperature to be used during leaching. In order to achieve the target lead concentration, the solid to liquid ratio is selected so that the suspension of MOPbM in the MSA solution includes from about 1 % solids to about 50% solids. - It is to be understood that the composition of the MSA solution may also be selected to match the target lead concentration. As an example, one molecule of MSA may be provided for each molecule of lead that is to be dissolved. It may also be desirable that excess MSA be present in order to maintain a minimum level of free acid in solution. As such, approximately 0.47 g of MSA may be used per gram of lead to be leached. In an example, if the mixed oxidized lead material MOPbM includes about 50% lead and the target concentration is 500 g of lead per liter of leachate, then the amount of MSA in the MSA solution may be about 118 g MSA/L. The amount of MSA may be calculated using the following equation: 500 g Pb/L x 50% (i.e., 50/100) x 0.47 g MSA/g Pb= 117.5 g MSA/L.
- The suspension of the mixed oxidized lead material MOPbM and MSA solution may be maintained at a predetermined temperature for a predetermined time as the liquid leachate is allowed to form. The predetermined temperature may range anywhere from about 10°C to about 100°C or the boiling point of water. In an example, the predetermined temperature ranges from about 10°C to about 80°C. In another example, the predetermined temperature may range anywhere from about 20°C to about 50°C. The temperature of the suspension may be increased to some temperature at the higher end of the given ranges in order to accelerate the rate and extent of the lead leaching. The time for maintaining the suspension may be any time that is sufficient to extract a desirable amount of the soluble lead from the mixed
oxidized lead material MOPbM. In an example, the time ranges from about 10 minutes to about 120 minutes. - While the liquid leachate is forming, the suspension may also be stirred. Stirring may be accomplished using any suitable mechanism including a baffle-stirred reactor, a magnetic stirrer, etc.
- The liquid leachate that is formed includes water and a lead-methane sulfonate salt that is soluble in the water. The lead-methane sulfonate salt is the product of acid leaching of the lead oxide and/or lead carbonate originally present in the mixed oxidized lead material MOPbM. Reactions that may take place during the formation of the liquid leachate include:
PbO + 2CH3SO3H → Pb(CH3SO3)2 + H2O
PbCO3 + 2CH3SO3H → Pb(CH3SO3)2 + H2O + CO2(g).
The first reaction involves the lead oxide (PbO) reacting with the methane sulfonic acid (CH3SO3H) to generate the lead-methane sulfonate salt (Pb(CH3SO3)2) and water. The second reaction involves the lead carbonate (PbCO3) reacting with the methane sulfonic acid (CH3SO3H) to generate the lead-methane sulfonate salt Pb(CH3SO3)2, water, and carbon dioxide (in gas form). - The liquid leachate may also include a solid material, i.e., a leach solid or residue. As such, the liquid leachate may be exposed to a solid-liquid separation process (shown at
reference numeral 14 ofFig. 1 ). Solid-liquid separation may be accomplished using thickening, filtration, centrifugation, cycloning, or another like technique in combination with washing. The solid-liquid separation results in the separation of the leach solid/residue from the liquid leachate. The use of the leach solid/residue will be discussed further hereinbelow in reference toreference numerals 22 through 26 ofFig. 1 . - After solid-liquid separation, the liquid leachate may still contain impurities. As such, the step shown at reference numeral 16 of
Fig. 1 involves purifying the liquid leachate. Reagent(s) R may be added to the liquid leachate in order to remove impurities I. Examples of the reagent R include pH adjusting agents or metallic lead powder or scrap. - In an example, purification of the liquid leachate is accomplished using pH Adjustment, with or without aeration, to oxidize and hydrolyze impurities, such as iron, aluminum, chromium, etc. In this example, suitable pH adjusting agents include lead carbonate, sodium hydroxide, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, and sodium carbonate. The pH adjusting agent may be added in any amount that is sufficient to achieve a desirable pH value. For example, the pH adjusting agent may be added to the liquid leachate until the pH of the leachate is at the target value. As an example, if iron carbonate is present in the mixed oxidized lead material MOPbM prior to MSA solution leaching, iron will extract with the lead into the liquid leachate, as shown in the following reaction:
FeCO3 + 2CH3SO3H → Fe(CH3SO3)2 + H2O + CO2(g).
- The iron can be removed by pH adjustment using an excess of lead carbonate and oxidation with air or oxygen. The removal of iron by pH adjustment is shown in the following reaction:
4Fe(CH3SO3)2 + O2(g + 2PbCO3 + 6H2O → 2(CH3SO3)2 + 4Fe(OH)3.
- In another example, cementation may be used to purify the liquid leachate. During cementation, metallic lead powder or scrap is used to precipitate other noble metals, such as copper. The amount of metallic lead powder or scrap used will depend, at least in part, on the amount of impurities to be removed. In an example, the amount of metallic lead powder or scrap is proportional to the amount of impurities to be removed. As such, it may be desirable to use near stoichiometric amounts. Depending upon the metal impurity to be removed, it may also be desirable to include an excess of the metallic lead powder or scrap (i.e., an amount above the stoichiometric amount).
- In still other examples, purification may also be accomplished with solvent extraction, ion exchange, or precipitation (e.g., sulfide precipitation) so as to remove the impurities I and produce a purified liquid leachate that is suitable for electrolysis.
- Solvent extraction may be accomplished by mixing an organic solution containing the extractant with the aqueous liquid leachate. Mixing extracts the impurity into the organic phase. The solvent extraction reagents may vary depending upon the type of impurity to be removed. Some examples of suitable solvent extraction reagents include di-2-ethyl-hexyl-phosphoric acid and similar phosphonic or phosphinic acids, salicylaldoxime, mixtures including salicylaldoxime, VERSATIC™ acids (i.e., highlybranched carbon-rich molecules with vinyl ester, glycidyl ester, acrylate, hydroxyl and/or carboxylic functionality, from Momentive Specialty Chemicals, Gahanna, OH), etc. After the organic solution and the aqueous liquid leachate are mixed, the two solutions are separated, for example, by gravity settling. At this point, the organic solution is loaded with the impurity, and this solution may be exposed to stripping. The purified aqueous liquid leachate may then be used in electrolysis.
- For liquid leachate purification via ion exchange, an ion exchange resin is contacted with the impure liquid leachate in a column or in a stirred reactor. Suitable ion exchange resins may include strong acid exchangers or chelating type exchangers. When precipitation is used to purify the liquid leachate, a chemical precipitant is added to the liquid leachate to precipitate the impurity as a solid particle. The solid particle impurities are removed using any suitable technique, such as filtering, thickening (e.g., gravity settling and washing), or the like. Examples of chemical precipitants that form sulfide precipitants include hydrogen sulfide gas, sodium hydrosulfide, calcium sulfide, sodium sulfide, etc.
- While various examples have been given herein, it is to be understood that any suitable purification method may be used to selectively remove impurities I that are present in the liquid leachate, so long as the soluble lead-methane sulfonate salt remains in solution.
- The purified liquid leachate is then exposed to electrolysis in order to recover lead. This is shown at
step 18 ofFig. 1 . As shown inFig. 2 , electrolysis may be accomplished in an undividedelectrochemical cell 30 containing ananode 32 and acathode 34. While asingle anode 32 andcathode 34 are shown, it is to be understood that asingle cell 30 may includemultiple anodes 32 andcathodes 34. Examples of materials suitable for theanodes 32 include graphite, titanium structures coated with precious metal oxides (i.e., DSA anodes), or any other anode material. Examples of materials suitable for thecathodes 34 include lead, stainless steel, similar recyclable materials, or any other cathode material. - The purified liquid leachate is introduced into the
cell 30 and functions as anelectrolyte 36. - The
electrodes power supply 38 via anexternal circuit 40. In operation, thepower supply 38 andcircuit 40 allow electric current and electrons (e-) to flow between theelectrodes anode 32 at a current density ranging from about 100 A/m2 to about 1000 A/m2. The current density may be varied depending, at least in part, on the configuration of thecell 30. - When the
cell 30 is operated, thepower supply 38 delivers direct current (DC) to theanode 32, and electrowinning is initiated. In electrowinning, the current is passed from theanode 32 through the purified liquid leachate (i.e., the electrolyte 36) which contains the lead. It is to be understood that ionic current flows in solution. Cations are attracted to thecathode 34 and anions are attracted to theanode 32, and thus are conducted by the voltage gradient in solution between theelectrodes cathode 34. The overall chemical reaction in thecell 30 is:
Pb(CH3SO3)2 + H2O → Pb + 2CH3SO3H + ½ O2(g)
where the following reactions take place at the anode and cathode, respectively:
H2O → ½ O2(g) + 2H+ + 2e-
Pb(CH3SO3)2 + 2e- → Pb + 2CH3SO3 -.
As illustrated in the chemical equations, lead is recovered as metal at thecathode 34 and oxygen is evolved at theanode 32 by electrolyzing the purified lead methane sulfonate solution (i.e., Pb(CH3SO3)2). - Upon completion of electrolysis (and electrowinning), the electrolyte 36 (i.e., the purified liquid leachate) is depleted of lead and contains methane sulfonic acid. At this point (reference numeral 20 in
Fig. 1 ) the lead-depleted, methanesulfonic acidcontaining electrolyte 36 may be recycled and used in the MSA solution in another cycle of lead recovery. When the recycled MSA is used in another cycle of lead recovery, some amount of concentrated MSA may be added in order to generate a new MSA solution including from about 0.01 wt.% methane sulfonic acid to about 30 wt.% methane sulfonic acid. - Electrolysis (and electrowinning) may be performed for any desirable amount of time in order to extract the lead from the
electrolyte 36. In an example, electroplating is allowed to take place for a period ranging from about 1 day to about 7 days. This may generate relatively thick deposits of pure lead on thecathode 34. - The temperature of the
cell 30 during electrolysis may range from ambient temperature (e.g., 20°C) to about 80°C. In an example, the temperature of thecell 30 is maintained from about 35°C to about 45°C. - Electrochemical additives, such as animal glue, lignin sulfonates, aloes, etc. may be added to the
cell 30 in order to smooth the cathode deposit and minimize contamination. The amount of any electrochemical additive added may be less than 1 g/L of solution and less than 1 kg/t (i.e., tonnes or metric tons) of metal plated. - Referring back to the step shown at
reference numeral 14 inFig. 1 , after the solid-liquid separation takes place, themethod 10 may further include additional steps in which the separated leach solid/residue is utilized. These additional steps may be particularly desirable when lead sulfate is present in the original mixed oxidized lead material MOPbM. The lead sulfate is not leached during acid leaching (i.e., at the step shown atreference numeral 12 inFig. 1 ), at least in part, because lead sulfate is essentially insoluble in the MSA solution. In the steps of themethod 10 shown atreference numerals 22. through 26, the lead sulfate may be converted to lead carbonate, which can be recycled in an MSA solution in another cycle of lead recovery. - At
reference numeral 22 inFig. 1 , the separated leach solid/residue that is recovered as a result of solid-liquid separation of the liquid leachate is treated with a source of soluble carbonate (shown as CO3 inFig. 1 ). Examples of the source of soluble carbonate include sodium carbonate, potassium carbonate, or ammonium carbonate. During this treatment, the leach solid/residue is pulped with an aqueous solution containing the soluble carbonate source. Pulping may be performed i) with a high solids density and a sufficient amount of the soluble carbonate, and ii) for a time and at a temperature so that lead sulfate phases/minerals in the leach solid/residue are converted to lead carbonate. In an example, the ratio of carbonate in solution to sulfate in the solids is at least 1: 1 on a mole: mole basis. An example of the reaction that may take place when the leach solid/residue (which contains lead sulfate, PbS04) is treated with sodium carbonate as the source of soluble carbonate is as follows:
PbSO4 + Na2CO3 → PbCO3 + Na2SO4.
- The treatment of the leach solid/residue generates a second liquid leachate which includes a second leach solid/residue. The second liquid leachate is a sulfate solution containing a lead carbonate solid (i.e., the second leach solid/residue). The second liquid leachate may be exposed to a solid-liquid separation process (shown at
reference numeral 24 ofFig. 1 ), which may be performed using any of the techniques previously described. The solid-liquid separation results in the separation of the second leach solid/residue from the second liquid leachate. - The sulfate solution (i.e., the second liquid leachate, shown as SO4 in
Fig. 1 ) may be used in any desirable manner. In the example provided above, the sodium sulfate solution may be sold as a separate by-product or used in other processes (such as in the manufacture of detergents, or in the Kraft process of paper pulping, etc.). - At this point (i.e., at
reference numeral 26 inFig. 1 ), the second leach solid/residue containing lead carbonate formed from lead sulfate may be recycled. For example, the second leach solid/residue may be incorporated into an MSA solution (with or without additional mixed oxidized lead material MOPbM) in another cycle of lead recovery. - To further illustrate the present disclosure, examples are given herein. It is to be understood that these examples are provided for illustrative purposes and are not to be construed as limiting the scope of the present disclosure.
- A lead concentrate containing 67.12% Pb, 0.03% Zn, 1.52% Fe, 1.57% Al, 11.12% C (inorganic) and 1.5% S (total) was obtained from the Magellan Mine (Australia). X-Ray Diffraction with Rietveld Analysis was performed to identify the minerals in the concentrate. This analysis revealed that the concentrate included 67.8% cerussite (PbCO3), 1 % galena (PbS), 10.3% anglesite (PbSO4), 7.1 % susannite (Pb4(CO3)2(SO4)(OH)2), 3.3% leadhillite (Pb4(CO3)2(SO4)(OH)2), 8% Quartz (SiO2) and 2.6% kaolinite (AlSi2O5(OH)4).
- The particle size of the lead concentrate was -150 + 7 4 microns (i.e., greater than 74 microns and less than 150 microns), and a solution having a methane sulfonic acid concentration of 0.036 mol/L was used. 2 g of the lead concentrate was added to 500 ml of the methane sulfonic acid solution in a 1 L baffled stirred reactor immersed in a water bath. The mixture was stirred at 400 rpm, and the temperature was set to 25°C. The mixture was allowed to sit under these conditions. A liquid leachate was formed, and a sample of the leachate was extracted after 30 minutes. This sample was analyzed for lead. This test revealed that after 30 minutes of leaching, 85% of the lead in the concentrate was extracted into solution.
- Residue from the liquid leachate was recovered and analyzed by Rietveld XRay Diffraction. The residue contained 0.5% cerussite, 1.5% galena, 62.4% anglesite, 24.5% quartz, 4.8% kaolinite, and 6.3% muscovite. These results confirm that the methane sulfonic acid leaching extracted most of the available lead from the concentrate.
- Another MSA leaching test was performed using 10 g of the lead concentrate described in Example 1, except that the particle size was -45 +38 microns (i.e., greater than 38 microns and less than 45 microns). The MSA solution of Example 1 was utilized, except that 50% excess MSA was added. This leaching test was performed at 25°C for 1 hour.
- A leach residue was recovered, washed, and dried. A sodium carbonate leaching process was performed for 1 hour at 50°C with 10:1 liquid to solid ratio and a 20% excess of sodium carbonate. A leach residue from this process was recovered, washed, and dried. The overall extraction of lead for this Example was 98.04%.
- It is to be understood that the ranges provided herein include the stated range and any value or sub-range within the stated range. For example, a range from about 10 µm to about 500 µm should be interpreted to include not only the explicitly recited limits of about 10 µm to about 500 µm, but also to include individual values, such as 15 µm, 120 µm, 250 µm, 400 µm, etc., and sub-ranges, such as from about 150 µm to about 450 µm, from about 200 µm to about 300 µm, etc. Furthermore, when "about" is utilized to describe a value, this is meant to encompass minor variations (up to+/- 10%) from the stated value.
- Reference throughout the specification to "one example", "another example", "an example", and so forth, means that a particular element (e.g., feature; structure, and/or characteristic) described in connection with the example is included in at least one example described herein, and may or may not be present in other examples. In addition, it is to be understood that the described elements for any example may be combined in any suitable manner in the various examples unless the context clearly dictates otherwise.
- It is to be understood use of the words "a" and "an" and other singular referents may include plural as well, both in the specification and claims, unless the context clearly indicates otherwise.
- While several examples have been described in detail, it will be apparent to Those skilled in the art that the disclosed examples may be modified. Therefore, the foregoing description is to be considered non-limiting.
Claims (10)
- A method for recovering lead from a mixed oxidized lead material, the method comprising:selecting methane sulfonic acid as a leaching acid for the mixed oxidized lead material;exposing the mixed oxidized lead material to a solution including the methane sulfonic acid, thereby leaching lead from any of a lead oxide or a lead carbonate in the mixed oxidized lead material, and generating a liquid leachate including a lead-methane sulfonate salt;purifying the liquid leachate; andrecovering lead from the purified liquid leachate using electrolysis.
- The method as defined in claim 1 wherein:the solution is an aqueous solution including from about 0.01 wt.% methane sulfonic acid to about 30 wt.% methane sulfonic acid; andthe mixed oxidized lead material is a lead ore or a lead concentrate.
- The method as defined in claim 2 wherein prior to exposing the mixed oxidized lead material to the aqueous solution, the method further comprises:identifying a target lead concentration for the liquid leachate; andselecting a composition of the aqueous solution to match the target lead concentration.
- The method as defined in claim 1 wherein exposing the mixed oxidized lead material to the solution including the methane sulfonic acid further generates a leach solid including lead sulfate, and wherein the method further comprises:separating the leach solid from the liquid leachate;treating the leach solid with a source of soluble carbonate, thereby generating a second leach solid including lead carbonate formed from the lead sulfate;removing a sulfate by-product from the second leach solid; andthen performing the exposing, the purifying, and the recovering with the second leach solid.
- The method as defined in claim 1, further comprising exposing the mixed oxidized lead material to a particle size reduction process prior to the exposing step, thereby generating particles of the mixed oxidized lead material having a particle size ranging from about 10 µm to about 500 µm.
- The method as defined in claim 1 wherein the exposing of the mixed oxidized lead material to the solution including the methane sulfonic acid includes:pulping the mixed oxidized lead material with the solution including the methane sulfonic acid to form a suspension; andmaintaining the suspension at a predetermined temperature ranging from about 10°C to about 100°C for a predetermined time.
- The method as defined in claim 1 wherein prior to the purifying step, the method further comprises performing a solid-liquid separation in order to separate solids from the liquid leachate.
- The method as defined in claim 1 wherein the purifying step is accomplished by one of:pH adjustment in combination with aeration;cementation with metallic lead;solvent extraction;ion exchange; orprecipitation.
- The method as defined in claim 1 wherein the electrolysis is accomplished by:introducing the purified liquid leachate to an undivided electrochemical cell containing an anode and a cathode; andpassing a current from the anode through the purified liquid leachate so that lead in the purified liquid leachate is electroplated onto the cathode;
and wherein:a density of the current ranges from about 100 A/m2 to about 1000 A/m2 anda temperature of the electrolysis ranges from about 20°C to about 80°C. - The method as defined in claim 9, further comprising adding an electrochemical additive to the undivided electrochemical cell.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL13812067T PL2920330T3 (en) | 2012-11-13 | 2013-11-13 | Recovering lead from a mixed oxidized material |
RS20180089A RS56991B1 (en) | 2012-11-13 | 2013-11-13 | Recovering lead from a mixed oxidized material |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261725824P | 2012-11-13 | 2012-11-13 | |
PCT/IB2013/002540 WO2014076547A1 (en) | 2012-11-13 | 2013-11-13 | Recovering lead from a mixed oxidized material |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2920330A1 EP2920330A1 (en) | 2015-09-23 |
EP2920330B1 true EP2920330B1 (en) | 2017-11-01 |
Family
ID=49880838
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13812067.0A Active EP2920330B1 (en) | 2012-11-13 | 2013-11-13 | Recovering lead from a mixed oxidized material |
Country Status (12)
Country | Link |
---|---|
US (1) | US9322104B2 (en) |
EP (1) | EP2920330B1 (en) |
JP (1) | JP6356137B2 (en) |
CN (1) | CN104039991B (en) |
AU (1) | AU2013346480B2 (en) |
CA (1) | CA2860614C (en) |
ES (1) | ES2657632T3 (en) |
MX (1) | MX364711B (en) |
PL (1) | PL2920330T3 (en) |
PT (1) | PT2920330T (en) |
RS (1) | RS56991B1 (en) |
WO (1) | WO2014076547A1 (en) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015077227A1 (en) * | 2013-11-19 | 2015-05-28 | Aqua Metals Inc. | Devices and methods for smelterless recycling of lead acid batteries |
AU2015350562B2 (en) * | 2013-11-19 | 2018-07-26 | Aqua Metals Inc. | Improved devices and method for smelterless recycling of lead acid batteries |
US9670565B2 (en) | 2014-06-20 | 2017-06-06 | Johnson Controls Technology Company | Systems and methods for the hydrometallurgical recovery of lead from spent lead-acid batteries and the preparation of lead oxide for use in new lead-acid batteries |
US9708689B2 (en) * | 2015-04-08 | 2017-07-18 | Honeywell International Inc. | Isotope displacement refining process for producing low alpha materials |
LT3294929T (en) | 2015-05-13 | 2021-11-10 | Aqua Metals Inc. | Closed loop systems and methods for recycling lead acid batteries |
CN107923057B (en) * | 2015-05-13 | 2020-07-14 | 艾库伊金属有限公司 | Electrodeposited lead compositions, methods of production and uses |
MX2017014539A (en) * | 2015-05-13 | 2018-03-12 | Aqua Metals Inc | Systems and methods for recovery of lead from lead acid batteries. |
CN106676578B (en) * | 2015-11-11 | 2018-09-28 | 沈阳有色金属研究院 | A kind of new and effective joint additive of Zinc electrolysis |
US10316420B2 (en) | 2015-12-02 | 2019-06-11 | Aqua Metals Inc. | Systems and methods for continuous alkaline lead acid battery recycling |
CN106498446A (en) * | 2016-10-20 | 2017-03-15 | 北京矿冶研究总院 | Lead sulfate suspension electrolysis method |
CN106756008B (en) * | 2017-02-22 | 2018-08-14 | 中南大学 | The method that two sections of adverse current atmospheric pressure oxidations of sulfonic acid solutions leach lead in concentrate of lead sulfide ore |
CN107227408B (en) * | 2017-04-28 | 2019-01-04 | 昆明理工大学 | A kind of low-temperature atmosphere-pressure Rapid Leaching method of siliceous concentrate of lead sulfide ore |
CN108754137A (en) * | 2018-08-02 | 2018-11-06 | 桐乡市思远环保科技有限公司 | The method that metallic lead is produced using solvent extraction electrodeposition process |
CN109097575B (en) * | 2018-09-10 | 2020-06-05 | 中国恩菲工程技术有限公司 | Method for extracting zinc element from low-grade lead-zinc ore |
CN110453077A (en) * | 2019-08-26 | 2019-11-15 | 湘潭大学 | A kind of method that scrap lead cream recycles |
CN113832344B (en) * | 2020-06-08 | 2022-06-14 | 中南大学 | Method for recovering copper and cobalt from copper-cobalt slag |
CN111926187A (en) * | 2020-08-19 | 2020-11-13 | 楚雄滇中有色金属有限责任公司 | Method for comprehensively recovering selenium, mercury, lead and silver from acid sludge |
CN114480862B (en) * | 2022-01-25 | 2024-01-30 | 长沙有色冶金设计研究院有限公司 | Method for recovering valuable elements from copper dross |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1752356A (en) * | 1927-01-14 | 1930-04-01 | Primos Lead Company | Process for reclaiming battery-plate material |
US2525942A (en) * | 1945-06-29 | 1950-10-17 | Standard Oil Co | Electrodepositing bath and process |
US3929597A (en) * | 1974-05-17 | 1975-12-30 | Hecla Mining Co | Production of lead and silver from their sulfides |
FI61721C (en) * | 1976-03-25 | 1982-09-10 | Lyijyvalkoistehd Groenberg Bly | SAETT ATT AOTERVINNA BLY AV BLYAVFALL |
JPS5411829A (en) * | 1977-06-30 | 1979-01-29 | Sumikou Ai Esu Pii Kk | Electolytical refining of lead |
JPS5493626A (en) * | 1978-01-06 | 1979-07-24 | Diamond Eng Co Ltd | Method of regenerating and recovering lead from leaddsulfateecontaining waste product |
US4181588A (en) * | 1979-01-04 | 1980-01-01 | The United States Of America As Represented By The Secretary Of The Interior | Method of recovering lead through the direct reduction of lead chloride by aqueous electrolysis |
US4272341A (en) * | 1980-01-09 | 1981-06-09 | Duval Corporation | Process for recovery of metal values from lead-zinc ores, even those having a high carbonate content |
IT1188203B (en) * | 1985-11-19 | 1988-01-07 | Tecneco Spa | HYDROMETALLURGIC PROCESS TO RECOVER IN LEAD METALLIC FORM THE LEAD CONTAINED IN THE ACTIVE MASS OF THE EXHAUSTED BATTERIES |
IT1191650B (en) * | 1986-01-09 | 1988-03-23 | Tecneco Spa | HYDROMETALLURGIC PROCESS FOR A TOTAL RECOVERY OF THE COMPONENTS OF EXHAUSTED LEAD ACID BATTERIES |
US4650553A (en) * | 1986-03-21 | 1987-03-17 | Pennwalt Corporation | Electrolytic recovery of lead from scrap |
IT1223314B (en) * | 1987-10-20 | 1990-09-19 | Engitec Impianti | HYDRO-METALLURGIC PROCESS TO RECOVER IN LEAD METALLIC FORM ALL THE LEAD CONTAINED IN THE ACTIVE MASS OF THE EXHAUSTED BATTERIES |
US4944851A (en) * | 1989-06-05 | 1990-07-31 | Macdermid, Incorporated | Electrolytic method for regenerating tin or tin-lead alloy stripping compositions |
IT1245449B (en) * | 1991-03-13 | 1994-09-20 | Ginatta Spa | HYDRO-METALLURGICAL PROCEDURE FOR THE PRODUCTION OF LEAD IN THE FORM OF METAL FROM MATERIALS CONTAINING OXIDES, PARTICULARLY FROM THE ACTIVE SUBSTANCE OF THE ACCUMULATORS |
US5262020A (en) * | 1991-03-13 | 1993-11-16 | M.A. Industries, Inc. | Hydrometallurgical method of producing metallic lead from materials containing oxides, particularly from the active material of accumulators |
US5494649A (en) * | 1991-10-03 | 1996-02-27 | Cognis, Inc. | Process for removing heavy metals from paint chips |
US5762683A (en) * | 1994-12-09 | 1998-06-09 | Asarco Incorporated | Ferric fluoborate/organic extractant hydrometallurgical process for recovering metals |
US5612224A (en) * | 1995-02-21 | 1997-03-18 | 21St Century Companies, Inc. | Method for measuring the quantity of lead on the surface of a brass component |
US5520794A (en) * | 1995-05-15 | 1996-05-28 | Elf Atochem North America, Inc. | Electrowinning of lead |
US5935409A (en) * | 1998-03-26 | 1999-08-10 | Asarco Incorporated | Fluoboric acid control in a ferric fluoborate hydrometallurgical process for recovering metals |
US6117209A (en) * | 1998-11-02 | 2000-09-12 | Gnb Technologies, Inc. | Hydrometallurgical process for treating alloys and drosses to recover the metal components |
US6428676B1 (en) * | 2000-11-08 | 2002-08-06 | Enthone Inc. | Process for producing low alpha lead methane sulfonate |
US7368043B2 (en) | 2003-04-10 | 2008-05-06 | Applied Intellectual Capital | Configurations and methods of electrochemical lead recovery from contaminated soil |
NZ570813A (en) * | 2006-03-01 | 2010-09-30 | Basf Se | Process for the acid digestion of metal-containing compounds |
ITVA20070007A1 (en) * | 2007-01-17 | 2008-07-18 | Millbrook Lead Recycling Techn | RECOVERY OF THE LEAD OF HIGH-PURITY CARBONATE UNIFORM PASTEL RECOVERY FROM THE CRUSHING OF EXHAUSTED LEAD ACCUMULATORS |
JP4798469B2 (en) * | 2009-03-23 | 2011-10-19 | Jx日鉱日石金属株式会社 | Carbonation method of lead |
JP2012072480A (en) | 2010-09-27 | 2012-04-12 | Jx Nippon Mining & Metals Corp | Method for selectively recovering indium from mixture of indium and tin |
CA2869431A1 (en) * | 2012-04-06 | 2013-10-10 | Entegris, Inc. | Removal of lead from solid materials |
-
2013
- 2013-11-11 US US14/076,564 patent/US9322104B2/en active Active
- 2013-11-13 CA CA2860614A patent/CA2860614C/en active Active
- 2013-11-13 CN CN201380004685.0A patent/CN104039991B/en active Active
- 2013-11-13 PT PT138120670T patent/PT2920330T/en unknown
- 2013-11-13 JP JP2015541251A patent/JP6356137B2/en active Active
- 2013-11-13 PL PL13812067T patent/PL2920330T3/en unknown
- 2013-11-13 RS RS20180089A patent/RS56991B1/en unknown
- 2013-11-13 AU AU2013346480A patent/AU2013346480B2/en active Active
- 2013-11-13 EP EP13812067.0A patent/EP2920330B1/en active Active
- 2013-11-13 WO PCT/IB2013/002540 patent/WO2014076547A1/en active Application Filing
- 2013-11-13 ES ES13812067.0T patent/ES2657632T3/en active Active
- 2013-11-13 MX MX2014009406A patent/MX364711B/en active IP Right Grant
Non-Patent Citations (1)
Title |
---|
None * |
Also Published As
Publication number | Publication date |
---|---|
CN104039991A (en) | 2014-09-10 |
EP2920330A1 (en) | 2015-09-23 |
CA2860614A1 (en) | 2014-05-22 |
RS56991B1 (en) | 2018-05-31 |
JP6356137B2 (en) | 2018-07-11 |
US9322104B2 (en) | 2016-04-26 |
US20140131219A1 (en) | 2014-05-15 |
ES2657632T3 (en) | 2018-03-06 |
MX364711B (en) | 2019-05-06 |
MX2014009406A (en) | 2014-11-10 |
JP2016502602A (en) | 2016-01-28 |
PT2920330T (en) | 2018-01-29 |
AU2013346480A1 (en) | 2014-07-24 |
WO2014076547A1 (en) | 2014-05-22 |
CA2860614C (en) | 2020-10-27 |
AU2013346480B2 (en) | 2017-08-31 |
PL2920330T3 (en) | 2018-05-30 |
CN104039991B (en) | 2018-03-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2920330B1 (en) | Recovering lead from a mixed oxidized material | |
US9322105B2 (en) | Recovering lead from a lead material including lead sulfide | |
CN100554452C (en) | Method for extracting copper from copper-containing sulfide ore by wet process | |
US9630844B2 (en) | Hydrometallurgical process for the recovery of tellurium from high lead bearing copper refinery anode slime | |
Hazotte et al. | Direct recovery of cadmium and nickel from Ni-Cd spent batteries by electroassisted leaching and electrodeposition in a single-cell process | |
US9683277B2 (en) | Process for preparing a ferric nitrate reagent from copper raffinate solution and use of such reagent in the leaching and/or curing of copper substances | |
US20040144208A1 (en) | Process for refining raw copper material containing copper sulfide mineral | |
EA005464B1 (en) | Method for recovering copper | |
JP5439997B2 (en) | Method for recovering copper from copper-containing iron | |
US9175411B2 (en) | Gold and silver extraction technology | |
JP5370777B2 (en) | Method for recovering copper from copper sulfide | |
CN113862479A (en) | Resource recovery processing method for lead plaster in waste lead storage battery | |
PL117268B1 (en) | Method of recovery of copper and accompanying metals from sulphide ores,post-flotation deposits and waste products in metallurgical processing of copper oresiz sernistykh rud,flotacionnykh osadkov i iz proizvodstvennykh otchodov metallurgicheskojj pererabotki mednykh rud | |
CN106566931B (en) | A kind of method that wet method using iron as recycled material refines lead | |
EP3575420A1 (en) | Bismuth purification method | |
CN112501451B (en) | Method for producing metallic lead by adopting solvent extraction electrodeposition process | |
JPS62500388A (en) | Production of zinc from ores and concentrates | |
CA1125227A (en) | Process for recovering cobalt electrolytically | |
Wu | Fundamental study on extracting lead from cerussite concentrate in methane sulfonic acid based solution | |
LI et al. | Fluorine-Free Electro-Refining of Crude Lead with High-Content Antimony in a Green Methanesulfonic Acid System |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20150615 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20160607 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20170511 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 942104 Country of ref document: AT Kind code of ref document: T Effective date: 20171115 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 5 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602013028861 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Ref document number: 2920330 Country of ref document: PT Date of ref document: 20180129 Kind code of ref document: T Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20180119 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2657632 Country of ref document: ES Kind code of ref document: T3 Effective date: 20180306 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 942104 Country of ref document: AT Kind code of ref document: T Effective date: 20171101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180201 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180301 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180201 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180202 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171130 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171130 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602013028861 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171113 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20171130 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171113 |
|
26N | No opposition filed |
Effective date: 20180802 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20131113 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20221123 Year of fee payment: 10 Ref country code: NL Payment date: 20221124 Year of fee payment: 10 Ref country code: IT Payment date: 20221122 Year of fee payment: 10 Ref country code: GB Payment date: 20221122 Year of fee payment: 10 Ref country code: FR Payment date: 20221122 Year of fee payment: 10 Ref country code: ES Payment date: 20221213 Year of fee payment: 10 Ref country code: DE Payment date: 20220527 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20231024 Year of fee payment: 11 Ref country code: RS Payment date: 20231024 Year of fee payment: 11 Ref country code: PT Payment date: 20231023 Year of fee payment: 11 Ref country code: IE Payment date: 20231117 Year of fee payment: 11 Ref country code: CZ Payment date: 20231113 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20231018 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: MK Payment date: 20231024 Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |